CN106435580B - 激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法 - Google Patents
激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法 Download PDFInfo
- Publication number
- CN106435580B CN106435580B CN201611058746.3A CN201611058746A CN106435580B CN 106435580 B CN106435580 B CN 106435580B CN 201611058746 A CN201611058746 A CN 201611058746A CN 106435580 B CN106435580 B CN 106435580B
- Authority
- CN
- China
- Prior art keywords
- powder
- molybdenum disulfide
- laser melting
- granularity
- melting coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims abstract description 43
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 37
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 230000008018 melting Effects 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000002844 melting Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005253 cladding Methods 0.000 claims abstract description 17
- 239000004411 aluminium Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000012790 confirmation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000010309 melting process Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 230000003026 anti-oxygenic effect Effects 0.000 abstract description 3
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 238000004372 laser cladding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 dense structure Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
本发明公开了一种激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法,包括以下组份:二硫化钼粉:3~8%wt,颗粒度0.1~2微米;铝粉:2~5%wt,颗粒度200~300微米;余量为镍粉,颗粒度50~100微米。本发明涉及的镍基二硫化钼粉末在激光熔覆过程中,有效控制二硫化钼的热分解,进而减小其分解对得到熔覆层的硫化作用,提高了熔覆层的抗氧化性能。
Description
技术领域
本发明涉及粉末材料领域,具体是指激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法。
背景技术
激光熔覆是指以不同的添料方式在被熔覆基体表面上放置被选择的涂层材料经激光辐照使之和基体表面一薄层同时熔化,并快速凝固后形成稀释度极低,与基体成冶金结合的表面涂层,显著改善基层表面的耐磨、耐蚀、耐热、抗氧化及电气特性的工艺方法,从而达到表面改性或修复的目的,既满足了对材料表面特定性能的要求,又节约了大量的贵重元素。与堆焊、喷涂、电镀和气相沉积相比,激光熔覆具有稀释度小、组织致密、涂层与基体结合好、适合熔覆材料多、粒度及含量变化大等特点,因此激光熔覆技术应用前景十分广阔。
二硫化钼是重要的固体润滑剂,特别适用于高温高压下。具有防潮、防水、防碱,防酸、等特性,并能够起到填充作用,由于二硫化钼的摩擦系数低,摩擦设备间产生的摩擦阻力小,可以节约电力消耗,能减小机械磨损,延长摩擦设备的使用寿命,减少设备零件的损耗,提高设备的出勤率,改善运行技术状况,延长检修周期,减轻了维修工人的劳动强度,节约劳动力。因此也被誉为“高级固体润滑油王”。而且采用二硫化钼润滑可以取消复杂的供油系统,大大简化了设备结构,相对提高了现在有效面积的利用率,同时,也将引起设备设计上的重大改革。然而,二硫化钼热稳定性差,无法直接应用于当前工业生产的等离子喷涂、电弧喷涂、火焰喷涂、激光熔覆等耐磨涂层制备行业,直接限制了其应用价值。
为此,本发明人在先申请了一项《激光熔覆用镍基二硫化钼耐磨复合膜层的电镀成膜液及其应用》,参见中国专利号:201310372688.1。该方案采用电镀工艺成膜,从而克服二硫化钼热稳定性差的温度。
但是该方案涉及的电镀制备预熔层所需时间过长,生产效率低,不适于产业化,限制了其应用范围和应用价值。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种适用于激光熔覆工艺成膜且减少二硫化钼在激光熔覆高温下大量分解问题的激光熔覆用镍基二硫化钼粉末。
本发明的第二个目的是提供一种激光熔覆用镍基二硫化钼粉末的制备方法。
本发明的第三个目的是提供一种激光熔覆用镍基二硫化钼粉末的使用方法。
为实现本发明的第一个目的,本发明的包括以下组份:
二硫化钼粉:3~8%wt,颗粒度0.1~2微米;
铝粉:2~5%wt,颗粒度200~300微米;
余量为镍粉,颗粒度50~100微米。
为实现本发明的第二个发明目的,其技术方案是包括有以下步骤:
(1)分别将已经经过颗粒度确认的二硫化钼粉末、铝粉、镍粉加入到乙醇溶液,搅拌成糊状,然后加入80%乙醇和20%甲醇的混合溶液中,浸泡10~30min,去除二硫化钼粉末、铝粉和镍粉表面带有污物;
(2)选用定量滤纸分别过滤,并分别置于120℃干燥箱中进行烘干处理,时间为30~60min,去除残留乙醇、甲醇;
(3)混粉,按所述比例称取二硫化钼粉末与铝粉,置于混粉机中,待混匀后,加入称量好的镍粉,混匀,得到激光熔覆用镍基二硫化钼粉末成品。
实现本发明的第三个发明目的,其技术方案是采用预铺粉法进行激光熔覆,其工艺参数:
激光能量:1000~2000W;
扫描速度:60~100m/h;
离焦量:正离焦3~5mm;
预铺粉厚度:0.5~2.0mm;
熔覆环境:惰性气体保护。
本发明的工艺有效控制二硫化钼的热分解,进而减小其分解对得到熔覆层的硫化作用,提高了熔覆层的抗氧化性能。
本发明的优点是:通过本发明的组分以及组分比例,其中,2~5%wt铝,能够实现以下效果:
(1)细化熔覆后过渡层的晶粒;
(2)减小熔覆过程中,二硫化钼分解对熔覆层的硫化作用;
(3)由于铝(熔点660℃)镍(熔点1453℃)的熔点差异,在熔覆过程中,实现熔覆粉末在熔凝过程中的梯度熔凝,且由于其的韧性高、导热好等特点,减少熔覆层裂纹的产生;
(4)提高熔覆过程的热传导效率,降低激光束辐照区域的温度,在提高得到熔覆层平整度的同时,减少二硫化钼的分解;
(5)提高得到熔覆层的抗氧化性能。
下面结合具体说明书附图和实施方式对本发明做进一步介绍。
附图说明
图1 本发明实施1预铺粉0.5mm激光熔覆后的横截面微观组织图。
具体实施方式
下面通过实施例对本发明进行具体的描述,只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限定,该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。
实施例1
该激光熔覆用镍基二硫化钼粉末包括以下组份:
二硫化钼:3%wt,颗粒度200微米;
铝:2%wt,颗粒度0.1微米;
余量为镍,颗粒度50微米。
其制备工艺是包括有以下步骤:
(1)分别将已经经过颗粒度确认的二硫化钼粉末、铝粉、镍粉加入到乙醇溶液,搅拌成糊状,然后加入80%乙醇和20%甲醇的混合溶液中,浸泡10-30min,去除二硫化钼粉末、铝粉和镍粉表面带有污物;
(2)选用定量滤纸分别过滤,并分别置于120℃干燥箱中进行烘干处理,时间为30-60min,去除残留乙醇、甲醇;
(3)混粉,按比例称取二硫化钼粉末与铝粉,置于混粉机中,待混匀后,加入称量好的镍粉,混匀,得到激光熔覆用镍基二硫化钼粉末成品。
该激光熔覆用镍基二硫化钼粉末用于激光熔覆工艺的使用方法是:采用预铺粉法进行激光熔覆,其工艺参数:
激光能量:1200W;
预铺粉0.5mm
扫描速度:80m/h;
离焦量:正离焦3mm;
预铺粉厚度:0.5mm;
熔覆环境:惰性气体保护。
其他实施例
下述各实施例的组分配置与实施例1不同,其制备方法和使用方法参考实施例1。
Claims (1)
1.一种激光熔覆用镍基二硫化钼粉末,其特征在于包括以下组份:
二硫化钼:3%wt,颗粒度200微米;
铝:2%wt,颗粒度0.1微米;
余量为镍,颗粒度50微米;
通过以下步骤制备:
(1)分别将已经经过颗粒度确认的二硫化钼粉末、铝粉、镍粉加入到乙醇溶液,搅拌成糊状,然后加入80%乙醇和20%甲醇的混合溶液中,浸泡10-30min,去除二硫化钼粉末、铝粉和镍粉表面带有污物;
(2)选用定量滤纸分别过滤,并分别置于120℃干燥箱中进行烘干处理,时间为30-60min,去除残留乙醇、甲醇;
(3)混粉,按比例称取二硫化钼粉末与铝粉,置于混粉机中,待混匀后,加入称量好的镍粉,混匀,得到激光熔覆用镍基二硫化钼粉末成品;
该激光熔覆用镍基二硫化钼粉末用于激光熔覆工艺的使用方法是:采用预铺粉法进行激光熔覆,其工艺参数:
激光能量:1200W;
预铺粉0.5mm
扫描速度:80m/h;
离焦量:正离焦3mm;
预铺粉厚度:0.5mm;
熔覆环境:惰性气体保护。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611058746.3A CN106435580B (zh) | 2016-11-25 | 2016-11-25 | 激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611058746.3A CN106435580B (zh) | 2016-11-25 | 2016-11-25 | 激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106435580A CN106435580A (zh) | 2017-02-22 |
CN106435580B true CN106435580B (zh) | 2019-04-23 |
Family
ID=58218665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611058746.3A Expired - Fee Related CN106435580B (zh) | 2016-11-25 | 2016-11-25 | 激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106435580B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109183027B (zh) * | 2018-10-26 | 2020-11-24 | 江苏理工学院 | 一种固体自润滑耐磨耐蚀复合涂层及其制备方法 |
CN111250900B (zh) * | 2020-02-24 | 2022-11-01 | 江西恒大高新技术股份有限公司 | 一种改性Inconel625粉末堆焊涂层的制备方法 |
CN111690928B (zh) * | 2020-06-28 | 2021-03-12 | 南京中科煜宸激光技术有限公司 | 锅炉水冷壁管排高效低稀释率涂层的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838758A (zh) * | 2010-05-24 | 2010-09-22 | 苏州大学 | 一种无钴镍基合金 |
CN102400080A (zh) * | 2011-11-28 | 2012-04-04 | 镇江中孚复合材料有限公司 | 一种制备自润滑深沟球轴承的方法 |
CN104233282A (zh) * | 2013-06-20 | 2014-12-24 | 沈阳大陆激光技术有限公司 | 一种用于内燃机涡轮增压器轮盘修复的镍基合金粉末 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8389129B2 (en) * | 2010-07-09 | 2013-03-05 | Climax Engineered Materials, Llc | Low-friction surface coatings and methods for producing same |
CN105209178B (zh) * | 2013-03-15 | 2018-09-07 | 梅索涂层公司 | 三元陶瓷热喷涂粉末和涂覆方法 |
-
2016
- 2016-11-25 CN CN201611058746.3A patent/CN106435580B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838758A (zh) * | 2010-05-24 | 2010-09-22 | 苏州大学 | 一种无钴镍基合金 |
CN102400080A (zh) * | 2011-11-28 | 2012-04-04 | 镇江中孚复合材料有限公司 | 一种制备自润滑深沟球轴承的方法 |
CN104233282A (zh) * | 2013-06-20 | 2014-12-24 | 沈阳大陆激光技术有限公司 | 一种用于内燃机涡轮增压器轮盘修复的镍基合金粉末 |
Non-Patent Citations (1)
Title |
---|
"激光熔覆制备MoS2/Ni基自润滑复合涂层组织及磨损性能";杨胶溪等;《金属热处理》;20100831;第35卷(第8期);第23页 |
Also Published As
Publication number | Publication date |
---|---|
CN106435580A (zh) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106435580B (zh) | 激光熔覆用镍基二硫化钼粉末、及其制备方法和使用方法 | |
Rogov et al. | AC plasma electrolytic oxidation of additively manufactured and cast AlSi12 alloys | |
Ramezani-Varzaneh et al. | Effects of phosphorus content on corrosion behavior of trivalent chromium coatings in 3.5 wt.% NaCl solution | |
CN103849911B (zh) | 一种用于低温制备光亮铝镀层的离子液体电镀液及其使用方法 | |
CN106149026A (zh) | 一种石墨烯/金纳米粒子复合材料的制备及表征方法 | |
CN101994147A (zh) | 一种金属基材表面处理的方法 | |
Heidari et al. | Electrodeposition of Cu–Sn alloys: theoretical and experimental approaches | |
CN104878382A (zh) | 一种激光熔覆用合金粉末及激光熔覆该粉末的方法 | |
US11827995B2 (en) | In-situ method for synthesizing Ni—w—Wc composite coating | |
Bahador et al. | Effect of power duty cycle on plasma electrolytic oxidation of A356-Nb2O5 metal matrix composites | |
Hwang et al. | Transient liquid phase bonding process using Sn-coated Cu dendritic particles | |
CN104313656A (zh) | 镍-钨-碳化硅-氧化铝复合电镀液及其制备方法和应用 | |
CN101367278A (zh) | 一种环保型自润滑材料 | |
CN104775118A (zh) | 一种激光熔覆粉末预置方法 | |
CN102002743B (zh) | 在纯铜或铜合金基体上熔盐电镀厚钨涂层的制备方法 | |
CN108070813B (zh) | 结晶器铜板表面耐腐蚀Cr3C2-NiCr-铝硅复合硅氧烷复合涂层的制备方法 | |
CN103215622B (zh) | 一种电线电缆铜导体电镀锡的方法 | |
Zhang et al. | Influence of additives on electroplated copper films and shear strength of SAC305/Cu solder joints | |
CN102554221B (zh) | 碳氢化合物包覆Ni基合金粉末及制备方法 | |
CN103805990B (zh) | 一种铜合金表面激光梯度熔覆合金粉末的方法 | |
Mohammadkhani et al. | Impact of density on the behavior of suspension plasma-sprayed TiB2 coatings in the presence of molten aluminum | |
Gugtapeh et al. | Formation of aluminum phosphate coating on graphite by cathodic electrochemical treatment | |
CN108359973A (zh) | 一种硅化物激光熔覆涂层材料及其制备方法 | |
Fu et al. | Study on electrodeposition behaviour and corrosion resistance of nickel-copper alloy in ChCl-EG deep eutectic solvents | |
CN103469285B (zh) | 激光熔覆用镍基二硫化钼耐磨复合膜层的电镀成膜液及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190423 |